Hexakis(1H-imidazole-κN3)mangan­ese(II) triaqua­tris(1H-imidazole-κN3)manganese(II) bis­(naphthalene-1,4-dicarboxyl­ate)

Li, J.-H.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536808011677

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m729

doi:10.1107/S1600536808011677

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Hexakis(1H-imidazole-κN³)manganese(II) triaquatris(1H-imidazole-κN³)manganese(II) bis(naphthalene-1,4-dicarboxylate)

Jun-Hua Li,^a Jing-Jing Nie ^a and Duan-Jun Xu ^a ^*

^aDepartment of Chemistry, Zhejiang University, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 17 April 2008; accepted 23 April 2008; online 26 April 2008)

In the crystal structure of the title compound, [Mn(C₃H₄N₂)₆][Mn(C₃H₄N₂)₃(H₂O)₃](C₁₂H₆O₄)₂, there are uncoordinated naphthalenedicarboxylate dianions and two kinds of Mn^II complex cations, both assuming a distorted octahedral geometry. One Mn^II cation is located on an inversion center and is coordinated by six imidazole molecules, while the other Mn^II cation is located on a twofold rotation axis and is coordinated by three water molecules and three imidazole units. The naphthalenedicarboxylate dianions are linked to both Mn^II complex cations via O—H⋯O and N—H⋯O hydrogen bonding, but no π–π stacking is observed between aromatic rings in the crystal structure.

Related literature

For general background, see: Su & Xu (2004 ); Liu et al. (2004 ). For a related structure, see: Derissen et al. (1979 ).

Experimental

Crystal data

[Mn(C₃H₄N₂)₆][Mn(C₃H₄N₂)₃(H₂O)₃](C₁₂H₆O₄)₂
M_r = 1205.0
Orthorhombic, P c c n
a = 29.605 (4) Å
b = 9.4619 (12) Å
c = 20.534 (3) Å
V = 5752.0 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 295 (2) K
0.33 × 0.30 × 0.18 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.790, T_max = 0.912
61105 measured reflections
5131 independent reflections
4174 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.135
S = 1.07
5131 reflections
367 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—N1	2.250 (3)
Mn1—N3	2.271 (2)
Mn1—N5	2.276 (2)
Mn2—N7	2.283 (3)
Mn2—N9	2.190 (4)
Mn2—O1W	2.265 (2)
Mn2—O2W	2.129 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O4	0.93	1.85	2.772 (3)	170
O1W—H1B⋯O1ⁱ	0.86	2.02	2.875 (3)	175
O2W—H2A⋯O3ⁱⁱ	0.85	1.78	2.624 (3)	172
N2—H2N⋯O4	0.86	1.87	2.730 (4)	176
N4—H4N⋯O2ⁱⁱⁱ	0.86	1.91	2.765 (3)	177
N6—H6N⋯O2^iv	0.86	1.95	2.810 (4)	178
N8—H8N⋯O1^v	0.86	2.02	2.870 (4)	167
N10—H10A⋯O3^vi	0.86	1.78	2.560 (7)	150
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, z]$ ; (iii) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y, -z+1; (v) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x+{\script{3\over 2}}, y, z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808011677/sg2237sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011677/sg2237Isup2.hkl

checkCIF report

Comment top

As part of our ongoing investigation on the nature of π-π stacking (Su & Xu, 2004; Liu et al., 2004), the title compound incorporating naphthalenedicarboxylate has recently been prepared and its crystal structure is reported here.

The crystal consists of uncoordinated naphthalenedicarboxylate dianions and two kinds of Mn^II complex cations. Both Mn^II complex cations assume distorted octahedral geometry (Table 1). The Mn1 is located on an inversion center and coordinated by six imidazole molecules, while the Mn2 is located about a twofold rotation axis and is coordinated by three water and three imidazole molecules (Fig. 1). The O2 (water) and N9 atoms are also located about the twofold axis, but the disordered N9-imidazole ring does not lie on the twofold axis. The naphthalenedicarboxylate dianion is not coordinated to the Mn^II cation but is linked to both Mn^II complex cations via O—H···O and N—H···O hydrogen bonding (Fig. 1 and Table 2). No π-π stacking is observed between adjacent naphthalene rings. Two carboxyl groups are twisted with respect to the naphthalene ring system with dihedral angles of 52.5 (3)° and 48.7 (3)°, which are larger than those found in the structure of free naphthalenedicarboxylic acid (ca 40°; Derissen et al., 1979).

Related literature top

For general background, see: Su & Xu (2004); Liu et al. (2004). For a related structure, see: Derissen et al. (1979).

Experimental top

An aqueous solution (10 ml) containing naphthalene-1,4-dicarboxyllic acid (0.108 g, 0.5 mmol) and sodium carbonate (0.053 g, 0.5 mmol) was refluxed for 0.5 h, then tetraaqua-manganese dichloride (0.099 g, 0.5 mmol) and imidazole (0.136 g, 2 mmol) were added to the above solution. After cooling to room temperature the solution was filtered. The single crystals of the title compound were obtained from the filtrate after 1 d.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound with 30% probability displacement (arbitrary spheres for H atoms). One of the disordered imidazole components is omitted for clarify. Dashed lines indicate hydrogen bonding [symmetry codes: (i) -x + 3/2, -y + 3/2, z; (ii) -x + 3/2, -y + 1/2, z + 1].

Hexakis(1H-imidazole-κN³)manganese(II) triaquatris(1H-imidazole-κN³)manganese(II) bis(naphthalene-1,4-dicarboxylate) top

Crystal data top

[Mn(C₃H₄N₂)₆][Mn(C₃H₄N₂)₃(H₂O)₃](C₁₂H₆O₄)₂	F(000) = 2496
M_r = 1205.0	D_x = 1.391 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 6856 reflections
a = 29.605 (4) Å	θ = 3.0–24.0°
b = 9.4619 (12) Å	µ = 0.51 mm⁻¹
c = 20.534 (3) Å	T = 295 K
V = 5752.0 (14) Å³	Prism, yellow
Z = 4	0.33 × 0.30 × 0.18 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	5131 independent reflections
Radiation source: fine-focus sealed tube	4174 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.2°, θ_min = 1.4°
ω scans	h = −35→35
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→10
T_min = 0.790, T_max = 0.912	l = −24→24
61105 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0611P)² + 4.7866P] where P = (F_o² + 2F_c²)/3
5131 reflections	(Δ/σ)_max = 0.001
367 parameters	Δρ_max = 1.06 e Å⁻³
5 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Mn(C₃H₄N₂)₆][Mn(C₃H₄N₂)₃(H₂O)₃](C₁₂H₆O₄)₂	V = 5752.0 (14) Å³
M_r = 1205.0	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 29.605 (4) Å	µ = 0.51 mm⁻¹
b = 9.4619 (12) Å	T = 295 K
c = 20.534 (3) Å	0.33 × 0.30 × 0.18 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	5131 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4174 reflections with I > 2σ(I)
T_min = 0.790, T_max = 0.912	R_int = 0.047
61105 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	5 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.07	Δρ_max = 1.06 e Å⁻³
5131 reflections	Δρ_min = −0.66 e Å⁻³
367 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0.5000	0.0000	0.5000	0.04145 (18)
Mn2	0.7500	0.7500	0.54180 (3)	0.04268 (18)
N1	0.53293 (9)	0.2142 (3)	0.50330 (12)	0.0505 (6)
N2	0.58426 (10)	0.3776 (3)	0.48747 (15)	0.0678 (8)
H2N	0.6061	0.4234	0.4696	0.081*
N3	0.54774 (8)	−0.0725 (3)	0.57988 (12)	0.0485 (6)
N4	0.58594 (9)	−0.2212 (3)	0.64106 (13)	0.0560 (7)
H4N	0.5943	−0.2989	0.6591	0.067*
N5	0.44833 (8)	0.0685 (3)	0.57579 (12)	0.0520 (6)
N6	0.41219 (10)	0.0705 (3)	0.66934 (14)	0.0634 (8)
H6N	0.4064	0.0574	0.7099	0.076*
N7	0.71986 (9)	0.9721 (3)	0.54032 (13)	0.0562 (7)
N8	0.69433 (10)	1.1818 (3)	0.56814 (17)	0.0687 (8)
H8N	0.6860	1.2514	0.5923	0.082*
O1	0.65926 (8)	0.0707 (2)	0.13121 (11)	0.0653 (6)
O2	0.60909 (8)	−0.0251 (2)	0.19895 (10)	0.0606 (6)
O3	0.69820 (10)	0.6144 (3)	0.35534 (12)	0.0948 (10)
O4	0.65304 (8)	0.5144 (3)	0.42532 (10)	0.0657 (7)
O1W	0.68093 (7)	0.6472 (2)	0.53876 (9)	0.0512 (5)
H1A	0.6718	0.6126	0.4983	0.077*
H1B	0.6757	0.5844	0.5679	0.077*
O2W	0.7500	0.7500	0.43813 (13)	0.0597 (8)
H2A	0.7658	0.8011	0.4125	0.090*
C1	0.56746 (13)	0.2553 (4)	0.46893 (18)	0.0675 (10)
H1	0.5792	0.2031	0.4345	0.081*
C2	0.56039 (16)	0.4160 (5)	0.5397 (3)	0.0967 (15)
H2	0.5651	0.4958	0.5653	0.116*
C3	0.52808 (14)	0.3172 (4)	0.5483 (2)	0.0817 (12)
H3	0.5059	0.3196	0.5804	0.098*
C4	0.55176 (11)	−0.2037 (3)	0.60003 (16)	0.0558 (8)
H4	0.5327	−0.2765	0.5869	0.067*
C5	0.60497 (13)	−0.0920 (4)	0.6489 (2)	0.0779 (11)
H5	0.6295	−0.0697	0.6753	0.094*
C6	0.58146 (12)	−0.0023 (4)	0.6111 (2)	0.0712 (10)
H6	0.5874	0.0938	0.6069	0.085*
C7	0.44988 (11)	0.0350 (4)	0.63811 (16)	0.0580 (8)
H7	0.4745	−0.0083	0.6579	0.070*
C8	0.38476 (13)	0.1312 (5)	0.6245 (2)	0.0810 (12)
H8	0.3560	0.1675	0.6318	0.097*
C9	0.40725 (12)	0.1289 (4)	0.56727 (19)	0.0736 (11)
H9	0.3962	0.1636	0.5280	0.088*
C10	0.71022 (13)	1.0575 (4)	0.58866 (18)	0.0663 (9)
H10	0.7140	1.0341	0.6323	0.080*
C11	0.69375 (15)	1.1776 (5)	0.5028 (2)	0.0842 (12)
H11	0.6844	1.2493	0.4749	0.101*
C12	0.70935 (15)	1.0492 (4)	0.4858 (2)	0.0819 (12)
H12	0.7125	1.0174	0.4432	0.098*
C20	0.65821 (10)	0.4142 (3)	0.31930 (14)	0.0459 (7)
C21	0.69273 (10)	0.3442 (4)	0.28942 (16)	0.0609 (9)
H21	0.7224	0.3681	0.2995	0.073*
C22	0.68436 (10)	0.2363 (4)	0.24350 (16)	0.0576 (9)
H22	0.7086	0.1916	0.2235	0.069*
C23	0.64154 (9)	0.1962 (3)	0.22789 (13)	0.0438 (6)
C24	0.60419 (9)	0.2703 (3)	0.25621 (13)	0.0406 (6)
C25	0.55847 (10)	0.2406 (3)	0.23935 (15)	0.0506 (7)
H25	0.5523	0.1678	0.2103	0.061*
C26	0.52392 (10)	0.3157 (4)	0.26466 (16)	0.0619 (9)
H26	0.4944	0.2929	0.2533	0.074*
C27	0.53196 (11)	0.4280 (4)	0.30797 (17)	0.0636 (9)
H27	0.5079	0.4804	0.3243	0.076*
C28	0.57517 (11)	0.4599 (3)	0.32607 (16)	0.0536 (8)
H28	0.5802	0.5339	0.3550	0.064*
C29	0.61259 (9)	0.3822 (3)	0.30145 (13)	0.0408 (6)
C30	0.67030 (11)	0.5228 (3)	0.37099 (15)	0.0523 (8)
C31	0.63602 (10)	0.0715 (3)	0.18193 (14)	0.0482 (7)
N9	0.7500	0.7500	0.64847 (19)	0.0789 (9)
N10	0.7681 (2)	0.7068 (7)	0.7487 (3)	0.0789 (9)	0.50
H10A	0.7842	0.7041	0.7834	0.095*	0.50
C13	0.78353 (16)	0.7509 (9)	0.6908 (2)	0.0789 (9)	0.50
H13	0.8131	0.7777	0.6819	0.095*	0.50
C14	0.7240 (2)	0.6669 (9)	0.7465 (3)	0.0789 (9)	0.50
H14	0.7053	0.6331	0.7794	0.095*	0.50
C15	0.71499 (17)	0.6904 (9)	0.6824 (3)	0.0789 (9)	0.50
H15	0.6874	0.6679	0.6633	0.095*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0469 (3)	0.0377 (4)	0.0398 (3)	0.0007 (3)	0.0026 (2)	0.0047 (3)
Mn2	0.0572 (4)	0.0383 (4)	0.0326 (3)	−0.0074 (3)	0.000	0.000
N1	0.0579 (15)	0.0432 (15)	0.0503 (15)	−0.0055 (12)	−0.0004 (12)	0.0041 (11)
N2	0.0686 (18)	0.0568 (19)	0.078 (2)	−0.0232 (15)	−0.0048 (16)	0.0047 (16)
N3	0.0525 (14)	0.0432 (15)	0.0498 (14)	0.0048 (11)	−0.0035 (11)	0.0045 (12)
N4	0.0600 (15)	0.0519 (17)	0.0560 (16)	0.0127 (13)	−0.0053 (13)	0.0106 (13)
N5	0.0556 (15)	0.0499 (15)	0.0506 (15)	0.0027 (12)	0.0090 (12)	0.0023 (12)
N6	0.0746 (18)	0.0633 (19)	0.0524 (16)	−0.0028 (15)	0.0200 (14)	−0.0069 (14)
N7	0.0631 (16)	0.0419 (15)	0.0637 (17)	−0.0015 (13)	0.0016 (13)	−0.0002 (13)
N8	0.0686 (18)	0.0457 (17)	0.092 (2)	0.0059 (14)	0.0175 (17)	−0.0035 (16)
O1	0.0891 (16)	0.0559 (14)	0.0509 (13)	−0.0123 (12)	0.0252 (12)	−0.0153 (11)
O2	0.0784 (15)	0.0518 (14)	0.0516 (13)	−0.0218 (12)	0.0107 (11)	−0.0151 (10)
O3	0.129 (2)	0.102 (2)	0.0540 (14)	−0.077 (2)	0.0049 (14)	−0.0151 (14)
O4	0.0837 (16)	0.0693 (16)	0.0441 (13)	−0.0292 (13)	0.0057 (11)	−0.0172 (11)
O1W	0.0607 (12)	0.0498 (13)	0.0431 (11)	−0.0133 (10)	0.0037 (9)	0.0033 (9)
O2W	0.082 (2)	0.065 (2)	0.0327 (14)	−0.0347 (17)	0.000	0.000
C1	0.080 (2)	0.056 (2)	0.066 (2)	−0.0206 (19)	0.0131 (19)	−0.0044 (18)
C2	0.106 (3)	0.059 (3)	0.125 (4)	−0.019 (2)	0.012 (3)	−0.031 (3)
C3	0.086 (3)	0.062 (2)	0.097 (3)	−0.013 (2)	0.020 (2)	−0.025 (2)
C4	0.0620 (19)	0.0449 (19)	0.061 (2)	−0.0002 (15)	−0.0067 (16)	0.0078 (15)
C5	0.076 (2)	0.061 (2)	0.097 (3)	0.003 (2)	−0.040 (2)	0.003 (2)
C6	0.073 (2)	0.047 (2)	0.093 (3)	−0.0006 (17)	−0.028 (2)	0.0060 (19)
C7	0.0611 (19)	0.065 (2)	0.0476 (18)	0.0006 (16)	0.0089 (15)	−0.0035 (16)
C8	0.067 (2)	0.091 (3)	0.085 (3)	0.021 (2)	0.025 (2)	0.000 (2)
C9	0.070 (2)	0.083 (3)	0.069 (2)	0.025 (2)	0.0110 (18)	0.013 (2)
C10	0.087 (3)	0.045 (2)	0.067 (2)	0.0017 (18)	0.0127 (19)	−0.0015 (17)
C11	0.097 (3)	0.065 (3)	0.091 (3)	0.026 (2)	−0.004 (2)	0.012 (2)
C12	0.112 (3)	0.067 (3)	0.067 (2)	0.024 (2)	−0.012 (2)	0.003 (2)
C20	0.0513 (16)	0.0452 (17)	0.0412 (15)	−0.0115 (13)	−0.0016 (12)	−0.0077 (13)
C21	0.0435 (16)	0.075 (2)	0.064 (2)	−0.0141 (16)	0.0012 (15)	−0.0213 (18)
C22	0.0449 (16)	0.068 (2)	0.0602 (19)	−0.0042 (15)	0.0068 (14)	−0.0221 (17)
C23	0.0480 (15)	0.0454 (16)	0.0381 (14)	−0.0061 (13)	0.0019 (12)	−0.0092 (13)
C24	0.0451 (14)	0.0417 (16)	0.0349 (14)	−0.0035 (12)	−0.0039 (11)	−0.0011 (12)
C25	0.0477 (16)	0.0563 (19)	0.0478 (16)	−0.0046 (14)	−0.0075 (13)	−0.0063 (15)
C26	0.0437 (17)	0.081 (2)	0.061 (2)	0.0022 (16)	−0.0135 (15)	−0.0003 (19)
C27	0.0534 (18)	0.073 (2)	0.065 (2)	0.0204 (17)	−0.0030 (16)	−0.0065 (18)
C28	0.0619 (19)	0.0467 (18)	0.0523 (18)	0.0082 (15)	−0.0063 (15)	−0.0082 (14)
C29	0.0477 (15)	0.0372 (15)	0.0376 (14)	−0.0013 (12)	−0.0026 (11)	−0.0007 (12)
C30	0.0614 (18)	0.0502 (19)	0.0452 (18)	−0.0130 (15)	−0.0087 (14)	−0.0049 (14)
C31	0.0528 (16)	0.0450 (18)	0.0468 (17)	−0.0051 (14)	−0.0005 (13)	−0.0089 (13)
N9	0.101 (2)	0.087 (2)	0.0486 (13)	0.0064 (19)	0.000	0.000
N10	0.101 (2)	0.087 (2)	0.0486 (13)	0.0064 (19)	0.000	0.000
C13	0.101 (2)	0.087 (2)	0.0486 (13)	0.0064 (19)	0.000	0.000
C14	0.101 (2)	0.087 (2)	0.0486 (13)	0.0064 (19)	0.000	0.000
C15	0.101 (2)	0.087 (2)	0.0486 (13)	0.0064 (19)	0.000	0.000

Geometric parameters (Å, º) top

Mn1—N1ⁱ	2.250 (3)	C4—H4	0.9300
Mn1—N1	2.250 (3)	C5—C6	1.344 (5)
Mn1—N3ⁱ	2.271 (2)	C5—H5	0.9300
Mn1—N3	2.271 (2)	C6—H6	0.9300
Mn1—N5ⁱ	2.276 (2)	C7—H7	0.9300
Mn1—N5	2.276 (2)	C8—C9	1.351 (5)
Mn2—N7ⁱⁱ	2.283 (3)	C8—H8	0.9300
Mn2—N7	2.283 (3)	C9—H9	0.9300
Mn2—N9	2.190 (4)	C10—H10	0.9300
Mn2—O1Wⁱⁱ	2.265 (2)	C11—C12	1.346 (6)
Mn2—O1W	2.265 (2)	C11—H11	0.9300
Mn2—O2W	2.129 (3)	C12—H12	0.9300
N1—C1	1.302 (4)	C20—C21	1.363 (4)
N1—C3	1.352 (4)	C20—C29	1.432 (4)
N2—C1	1.316 (4)	C20—C30	1.521 (4)
N2—C2	1.335 (5)	C21—C22	1.412 (4)
N2—H2N	0.8600	C21—H21	0.9300
N3—C4	1.314 (4)	C22—C23	1.362 (4)
N3—C6	1.360 (4)	C22—H22	0.9300
N4—C4	1.327 (4)	C23—C24	1.433 (4)
N4—C5	1.356 (5)	C23—C31	1.520 (4)
N4—H4N	0.8600	C24—C25	1.425 (4)
N5—C7	1.319 (4)	C24—C29	1.430 (4)
N5—C9	1.355 (4)	C25—C26	1.350 (4)
N6—C7	1.330 (4)	C25—H25	0.9300
N6—C8	1.355 (5)	C26—C27	1.406 (5)
N6—H6N	0.8600	C26—H26	0.9300
N7—C10	1.312 (4)	C27—C28	1.366 (5)
N7—C12	1.372 (5)	C27—H27	0.9300
N8—C10	1.335 (5)	C28—C29	1.423 (4)
N8—C11	1.342 (5)	C28—H28	0.9300
N8—H8N	0.8600	N9—C13	1.3195 (10)
O1—C31	1.248 (3)	N9—C13ⁱⁱ	1.3195 (10)
O2—C31	1.262 (4)	N9—C15ⁱⁱ	1.3703 (10)
O3—C30	1.239 (4)	N9—C15	1.3703 (10)
O4—C30	1.230 (4)	N10—C13	1.3400 (10)
O1W—H1A	0.9331	N10—C14	1.3597 (11)
O1W—H1B	0.8576	N10—H10A	0.8600
O2W—H2A	0.8542	C13—H13	0.9300
C1—H1	0.9300	C14—C15	1.3603 (11)
C2—C3	1.349 (6)	C14—H14	0.9300
C2—H2	0.9300	C15—H15	0.9300
C3—H3	0.9300

N1ⁱ—Mn1—N1	180.00 (12)	C5—C6—N3	110.1 (3)
N1ⁱ—Mn1—N3ⁱ	88.89 (9)	C5—C6—H6	124.9
N1—Mn1—N3ⁱ	91.11 (9)	N3—C6—H6	124.9
N1ⁱ—Mn1—N3	91.11 (9)	N5—C7—N6	112.2 (3)
N1—Mn1—N3	88.89 (9)	N5—C7—H7	123.9
N3ⁱ—Mn1—N3	180.00 (8)	N6—C7—H7	123.9
N1ⁱ—Mn1—N5ⁱ	90.80 (9)	C9—C8—N6	106.8 (3)
N1—Mn1—N5ⁱ	89.20 (9)	C9—C8—H8	126.6
N3ⁱ—Mn1—N5ⁱ	90.60 (9)	N6—C8—H8	126.6
N3—Mn1—N5ⁱ	89.40 (9)	C8—C9—N5	109.7 (3)
N1ⁱ—Mn1—N5	89.20 (9)	C8—C9—H9	125.2
N1—Mn1—N5	90.80 (9)	N5—C9—H9	125.2
N3ⁱ—Mn1—N5	89.40 (9)	N7—C10—N8	112.4 (3)
N3—Mn1—N5	90.60 (9)	N7—C10—H10	123.8
N5ⁱ—Mn1—N5	180.00 (9)	N8—C10—H10	123.8
O2W—Mn2—N9	180.000 (1)	N8—C11—C12	106.4 (4)
O2W—Mn2—O1Wⁱⁱ	88.42 (5)	N8—C11—H11	126.8
N9—Mn2—O1Wⁱⁱ	91.58 (5)	C12—C11—H11	126.8
O2W—Mn2—O1W	88.42 (5)	C11—C12—N7	110.2 (4)
N9—Mn2—O1W	91.58 (5)	C11—C12—H12	124.9
O1Wⁱⁱ—Mn2—O1W	176.85 (10)	N7—C12—H12	124.9
O2W—Mn2—N7ⁱⁱ	89.24 (7)	C21—C20—C29	119.3 (3)
N9—Mn2—N7ⁱⁱ	90.76 (7)	C21—C20—C30	117.8 (3)
O1Wⁱⁱ—Mn2—N7ⁱⁱ	92.42 (9)	C29—C20—C30	122.9 (3)
O1W—Mn2—N7ⁱⁱ	87.54 (9)	C20—C21—C22	121.3 (3)
O2W—Mn2—N7	89.24 (7)	C20—C21—H21	119.3
N9—Mn2—N7	90.76 (7)	C22—C21—H21	119.3
O1Wⁱⁱ—Mn2—N7	87.54 (9)	C23—C22—C21	121.5 (3)
O1W—Mn2—N7	92.42 (9)	C23—C22—H22	119.3
N7ⁱⁱ—Mn2—N7	178.48 (14)	C21—C22—H22	119.3
C1—N1—C3	103.8 (3)	C22—C23—C24	119.1 (3)
C1—N1—Mn1	126.4 (2)	C22—C23—C31	117.6 (3)
C3—N1—Mn1	128.6 (2)	C24—C23—C31	123.3 (2)
C1—N2—C2	105.8 (3)	C25—C24—C29	118.0 (3)
C1—N2—H2N	127.1	C25—C24—C23	122.5 (3)
C2—N2—H2N	127.1	C29—C24—C23	119.4 (2)
C4—N3—C6	104.3 (3)	C26—C25—C24	121.5 (3)
C4—N3—Mn1	124.7 (2)	C26—C25—H25	119.3
C6—N3—Mn1	130.6 (2)	C24—C25—H25	119.3
C4—N4—C5	106.3 (3)	C25—C26—C27	120.9 (3)
C4—N4—H4N	126.9	C25—C26—H26	119.6
C5—N4—H4N	126.9	C27—C26—H26	119.6
C7—N5—C9	104.9 (3)	C28—C27—C26	119.9 (3)
C7—N5—Mn1	124.8 (2)	C28—C27—H27	120.1
C9—N5—Mn1	129.4 (2)	C26—C27—H27	120.1
C7—N6—C8	106.4 (3)	C27—C28—C29	121.2 (3)
C7—N6—H6N	126.8	C27—C28—H28	119.4
C8—N6—H6N	126.8	C29—C28—H28	119.4
C10—N7—C12	103.9 (3)	C28—C29—C24	118.6 (3)
C10—N7—Mn2	130.0 (2)	C28—C29—C20	122.3 (3)
C12—N7—Mn2	126.1 (2)	C24—C29—C20	119.1 (2)
C10—N8—C11	107.1 (3)	O4—C30—O3	123.9 (3)
C10—N8—H8N	126.5	O4—C30—C20	119.4 (3)
C11—N8—H8N	126.5	O3—C30—C20	116.7 (3)
Mn2—O1W—H1A	116.0	O1—C31—O2	125.1 (3)
Mn2—O1W—H1B	116.3	O1—C31—C23	117.6 (3)
H1A—O1W—H1B	109.0	O2—C31—C23	117.3 (3)
Mn2—O2W—H2A	128.0	C13—N9—C15	103.7 (4)
N1—C1—N2	113.7 (3)	C13—N9—Mn2	131.2 (3)
N1—C1—H1	123.1	C15—N9—Mn2	120.6 (3)
N2—C1—H1	123.1	C13—N10—C14	112.6 (6)
N2—C2—C3	107.0 (4)	C13—N10—H10A	123.7
N2—C2—H2	126.5	C14—N10—H10A	123.7
C3—C2—H2	126.5	N9—C13—N10	109.0 (5)
C2—C3—N1	109.5 (4)	N9—C13—H13	125.5
C2—C3—H3	125.2	N10—C13—H13	125.5
N1—C3—H3	125.2	N10—C14—C15	100.0 (6)
N3—C4—N4	112.7 (3)	N10—C14—H14	130.0
N3—C4—H4	123.6	C15—C14—H14	130.0
N4—C4—H4	123.6	C14—C15—N9	114.3 (5)
C6—C5—N4	106.6 (3)	C14—C15—H15	122.9
C6—C5—H5	126.7	N9—C15—H15	122.9
N4—C5—H5	126.7

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O4	0.93	1.85	2.772 (3)	170
O1W—H1B···O1ⁱⁱⁱ	0.86	2.02	2.875 (3)	175
O2W—H2A···O3ⁱⁱ	0.85	1.78	2.624 (3)	172
N2—H2N···O4	0.86	1.87	2.730 (4)	176
N4—H4N···O2^iv	0.86	1.91	2.765 (3)	177
N6—H6N···O2ⁱ	0.86	1.95	2.810 (4)	178
N8—H8N···O1^v	0.86	2.02	2.870 (4)	167
N10—H10A···O3^vi	0.86	1.78	2.560 (7)	150

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, −y+3/2, z; (iii) x, −y+1/2, z+1/2; (iv) x, −y−1/2, z+1/2; (v) x, −y+3/2, z+1/2; (vi) −x+3/2, y, z+1/2.

Experimental details

Crystal data
Chemical formula	[Mn(C₃H₄N₂)₆][Mn(C₃H₄N₂)₃(H₂O)₃](C₁₂H₆O₄)₂
M_r	1205.0
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	295
a, b, c (Å)	29.605 (4), 9.4619 (12), 20.534 (3)
V (Å³)	5752.0 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.33 × 0.30 × 0.18

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.790, 0.912
No. of measured, independent and observed [I > 2σ(I)] reflections	61105, 5131, 4174
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.135, 1.07
No. of reflections	5131
No. of parameters	367
No. of restraints	5
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.06, −0.66

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Mn1—N1	2.250 (3)	Mn2—N9	2.190 (4)
Mn1—N3	2.271 (2)	Mn2—O1W	2.265 (2)
Mn1—N5	2.276 (2)	Mn2—O2W	2.129 (3)
Mn2—N7	2.283 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O4	0.93	1.85	2.772 (3)	170
O1W—H1B···O1ⁱ	0.86	2.02	2.875 (3)	175
O2W—H2A···O3ⁱⁱ	0.85	1.78	2.624 (3)	172
N2—H2N···O4	0.86	1.87	2.730 (4)	176
N4—H4N···O2ⁱⁱⁱ	0.86	1.91	2.765 (3)	177
N6—H6N···O2^iv	0.86	1.95	2.810 (4)	178
N8—H8N···O1^v	0.86	2.02	2.870 (4)	167
N10—H10A···O3^vi	0.86	1.78	2.560 (7)	150

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+3/2, −y+3/2, z; (iii) x, −y−1/2, z+1/2; (iv) −x+1, −y, −z+1; (v) x, −y+3/2, z+1/2; (vi) −x+3/2, y, z+1/2.

Acknowledgements

The work was supported by the ZIJIN project of Zhejiang University, China.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Derissen, J. L., Timmermans, C. & Schoone, J. C. (1979). Cryst. Struct. Commun. 8, 533–536. CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Liu, B.-X., Su, J.-R. & Xu, D.-J. (2004). Acta Cryst. C60, m183–m185. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, J.-R. & Xu, D.-J. (2004). J. Coord. Chem. 57, 223–229. Web of Science CSD CrossRef CAS Google Scholar

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